Process for the manufacture of polymeric materials with a high chemical and mechanical resistance and polymeric materials with a high chemical and mechanical resistance

ABSTRACT

A process for the manufacture of materials with a high chemical and mechanical resistance in which for each 100 parts by volume of vinylester resin treated with 0.85-1.47 parts by volume of an accelerant in the form of cobalt naphthenate, there are added at least in two batches 50-900 parts by volume of an inorganic filler constituting previously roasted at a temperature not lower than 470 K disintegrated to a particle size of at least 30 μm phosphogypsum or a composition of phosphogypsum with glass-forming oxides or phosphogypsum with magnetite or phosphogypsum with microsphere, after which on continuous stirring there is added, if necessary, up to 60 parts by volume of styrene and/or up to 0.2 parts by volume of dimethylaniline, and then the whole is polymerized in the presence of know initiators such as organic peroxides. The materials with a high chemical and mechanical resistance constitute polymerized composition of synthetic resin and inorganic fillers, consisting of 7.5-88.1% by weight of vinylester resin, styrene and/or a low-molecular-weight unsaturated polyester resin in a quantity up to 34.1% by weight, and 14.3-86.6% by weight of phosphogypsum or 0.4-46.6% by weight of phosphogypsum and 6.4-44.8% by weight of glass-forming oxides or 4.6-53.5% by weight of microsphere or 5.5-42.1% by weight of magnetite. The process for the manufacture of these materials makes it possible to utilize industrial wastes resulted from production of phosphoric acid, while the material itself in all its varieties is characterized by a very good resistance to aggressive media, also at elevated temperatures, and suitable for processing by mechanical methods as well as for combining with other materials by using to that end an incompletely polymerized composition of the material.

The subject of this invention is a process for the manufacture ofpolymeric materials with a high chemical and mechanical resistance,particularly suitable in chemical, electrochemical and non-ferrousmetals industries, as well as a polymeric material with a high chemicaland mechanical resistance.

It is commonly known that synthetic resins are used either as binders inbuilding materials such as mortars and concretes or as components ofchemo- or thermosetting composites containing in their compositionfillers being many a time industrial wastes such as sawdust andsmoke-box ashes. Thus, Polish Patent Specification no. 65 677 disclosesa floor mix containing 30-40% of polyester resins, about 5% of epoxideresins, 55-65% of mineral fillers and an accelerant and hardener, thewhole showing a mass density of 2.2 kg/dm³. There is also known a floormix containing 100 parts of epoxide resins, 5-20 parts vegetable epoxyoil, 10-20 parts of xylene, 8-12 parts of triethanolamine, 200-400 partsof kermesite with a grain size of up to 5 mm and 20-150 parts of drymicrospheres with a bulk density of 0.35-0.42 kg/dm³, thermalconductivity 0.04-0.1 W/mK and compression strength 30-35 MPa. There arealso commonly known problems in utilization of industrial wastes,including waste phosphogypsum resulted in considerable amounts from themanufacture of phosphoric acid from apatites. One of the utilizationprocesses; in accordance with Polish Patent Specification no. 119 692,consists of elimination of radium, uranium, fluorine and phosphorouscompounds from phosphogypsum through decomposition by means ofphosphoric acid. Another process, according to Polish Patent Applicationno. P. 287 016, concerns the manufacture of gypsum from wastephosphogypsum by adding about 6 parts by weight of waste ferroussulphate and about 4.7 parts by weight of barium chloride to 1000 partsby weight of waste phosphogypsum, and then calcinating the mixture withquicklime at temperature 350-500 K. Another Polish Patent Specificationno. 147 599 discloses the manufacture of building phosphogypsummaterials comprising the preparation of a binding slurry by mixing athermally treated phosphogypsum with make-up water and addingantiefflorescent agents in the form of sulphonated polycondensatingresins, organic and inorganic silicon salts alkali metals. It is alsoknown from Polish Patent Application no. P. 283 240 that wastephosphogypsum can be combined with polyester resins to prepare amaterial which is characterizes by good mechanical and chemicalresistance and low water and oil absorptions. According to Polish PatentApplication no. P. 299 472 and P. 299 473, it is also possible tocombine, in an anhydrous system, epoxide resins and/or polyester resinswith phosphogypsum or phosphogypsum and glass-forming oxides orphosphogypsum and magnetite to prepare ceramic-like materials withspecial properties including good mechanical and chemical resistance,being easily formable, especially by casting, and showing good adherenceto various materials such as wood, metals, glass, and susceptible toprocessing by machining, grinding and cutting, and suitable for a wideapplication. There is also known from U.S. Pat. No. 3,873,492 a processfor the manufacture of a mixed materials containing gypsum and athermoplastic resin; the gypsum to be used for the mixture is previouslypowdered and impregnated with a polysulphone resin.

It has unexpectedly appeared that using waste phosphogypsum, but onlyafter its previous thermal treatment, in a composition with vinylesterresins, one can prepare materials with a very high resistance both toacidic and alkaline media, showing water absorption below 0.5%, Charpyimpact strength over 1.55 kJ/m², bending strength over 15 MPa,compression strength over 75 MPa, thermal conductivity index below 0.485W/mK, the materials being also safe to health and showing aradioactivity level corresponding to that of cement and red bricks.Moreover, when glass-forming oxides are added to the materials they arecharacterized by ability to absorb X-radiation with an energy of 45-55keV and hard radiation with an energy of 0.6-1.25 MeV; if magnetite isadded to the composition, the materials show magnetic properties andwhen microsphere is added to the composition, the resultant material ischaracterized by a low thermal conductivity and a density of below 0.8kg/dm³.

The process for the manufacture of materials with a high chemical andmechanical resistance by polymerization of a mixture of a syntheticresin with an inorganic filler in the presence of accelerants andpolymerization initiators, in an anhydrous medium, according to thepresent invention consists in that to each 100 parts by volume ofvinylester resin, treated with 0.85-1.47 parts by volume of anaccelerant in the form of a styrene solution of cobalt naphthenate,50-900 parts by volume of waste phosphogypsum previously roasted at atemperature not lever than 470 K and disintegrated to a particle size ofbelow 30 μm, with a bulk density of 0.71-0.93 kg/dm³, are added whilecontinuous stirring, at least in two batches, and if necessary up to 60parts by volume of styrene and/or a low-molecular-weight unsaturatedpolyester resin and/or up to 0.2 parts by volume of dimethylaniline arealso added. Next, on continuous stirring, to the physicochemicallyhomogenized composition a known organic peroxide in a quantity of6.3-7.3 parts by volume is added as polymerization initiator, to obtain130-780 parts by volume of a material resistant to the action of acidsand bases, both concentrated and diluted ones, with an impact strengthof over 1.85 kJ/m², bending strength over 35.4 MPa, compression strengthover 106 MPa and water absorption below 0.61%. The resultant material,due to its properties, is perfectly suitable to make floors in rooms,including also accommodations under conditions occuring in chemical andelectrochemical industries and in non-ferrous metal works, especially indepartments of electrolytic refining.

In order to obtain the material in a form suitable for application,especially by the hydrodynamic method, as anticorrosive or protectivecoats, the physicochemically homogenized composition of vinylester resinwith phosphogypsum is additionally processed similarly as in themanufacture of paints and lacquers, preferably in fine grinding millswith continuous operation, until the particle size in the composition isbelow 7 μm, then styrene in a quantity of up to 2.5% by volume and/or alow-molecular-weight unsaturated polyester resin in a quantity of up to5% in relation to the volume of the whole mixture are added. Next,polymerization initiators are added to produce a material suitable forspraying onto surfaces and allowing in a single spray the formation of acoat with a thickness of at least 250 μm, which means a coat thicknessfeasible in using known coats not before at least two and usually fouror five spraying runs.

The material with a high chemical and mechanical resistance,constituting a polymerized composition of synthetic resin and aninorganic filler, according to the present invention consists of11.6-77.1% by weight of vinylester resin, 14.3-86.8% by weight of wastephosphogypsum, 0.67-3.74% by weight of an organic peroxide and up to 29%by weight of styrene and/or a low-molecular-weight unsaturated polyesterresin.

A modification of the process for the manufacture of the materialaccording to the present invention consists in adding, as an inorganicfiller, at least in two batches, either previously roasted phosphogypsumalternately with glass-forming oxides or a physically homogenized drycomposition or roasted phosphogypsum and glass-forming oxides consistingmainly of lead, silicon and barium oxides with particle size up to 25 μmand a bulk density of 3.9-4.1 kg/dm³, with the weight ratio ofphosphogypsum to glass-forming oxides being as 1:0.7-1.5. The additionof glass-forming oxides as a component to the inorganic filler makes itpossible to produce a material which is capable to attenuate or absorbX-radiation with an energy of 0.55 keV and hard radiation with an energyof 0.6-1.25 MeV. In the case when the material is to be used asprotective coating capable to attenuate or absorb the above mentionedradiation, the physicochemically composition of vinylester resin withphosphogypsum is additionally processed similarly as in manufacturingpaints and lacquers, preferably in continuously operated fine grindingmills until the particle size is 7 μm and then 2.5% by volume of styreneand/or up to 5% by volume of a low-molecular-weight unsaturatedpolyester resin are added, after which polymerization initiators areadded. The resultant material is characterized by a very good fluidityat the initial stage of polymerization, which facilitates its use forcoating elements to be used as shields or screens protecting againstradiation and requiring anticorrosive protection.

The material capable to attenuate and/or to absorb X-radiation with anenergy of 55 keV and hard radiation with an energy of 0.6-1.25 MeV,constituting a polymerized composition of a synthetic resin and aninorganic filler, according to the present invention consists of10.1-79.8% by weight of vinylester resin, 5.8-43.9% by weight of roastedwaste phosphogypsum, 6.4-44.8% by weight of glass-forming oxides,containing mainly lead, silicon and barium oxides, 0.58-3.89% by weightof an organic peroxide and up to 29.8% by weight of styrene and/or alow-molecular-weight unsaturated polyester resin.

Another modification of the process for the manufacture of the materialaccording to the present invention consists in that there is added as aninorganic filler, at least in two batches, either previously roastedphosphogypsum alternately with a microsphere or a previously physicallyhomogenized dry composition of roasted phosphogypsum and microsphere,with a particle size of below 25 μm, with the weight ratio ofphosphogypsum to microsphere being as 1:0.43-45. In order to prepare amaterial in a form suitable for applying as anticorrosive or protectivecoats, an inorganic filler with a particle size of below 7 μm is used.The addition of microsphere as a component of the inorganic filler makesit possible to produce a material also with density of below 0.8 kg/dm³,being very resistant to chemical nad showing thermal conductivity below0.24 W/mK, water absorption below 0.24%, which is particularly suitablefor use in yacht--and shipbuilding industry, including protective andanticorrosive coatings.

The material in the form of a polymerized composition of a syntheticresin and an inorganic filler, according to the present inventionconsists of 7.5-88.1% by weight of vinylester resin, 0.4-38.2% by weightof roasted waste phosphogypsum, 4.6-53.5% by weight of microsphere,0.43-4.40% by weight of an organic peroxide and 34.1% by weight ofstyrene and/or a low-molecular-weight unsaturated polyester resin.

Still another modification of the process for the manufacture of thematerial according to the present invention consists in adding, as aninorganic filler at least in two batches, either previously roastedwaste phosphogypsum alternately with magnetite or a physicallyhomogenized dry composition of previously roasted phosphogypsum andmagnetite, with the weight ratio of phosphogypsum to magnetite being as1:0.6-1.3. In order to produce a material suitable for hydrodynamicapplication, the physicochemically homogenized composition of vinylesterresin, phosphogypsum and magnetite is processed similarly as in themanufacture of paints and lacquers, preferably by grinding incontinuously operated mills. The resultant material, due to its highchemical resistance and very good mechanical properties as well asmagnetic properties, is perfectly suitable for using inmicroelectronics, especially for manufacturing electronic microelementsto be exposed to corroding media.

The material in the form of a polymerized composition of a syntheticresin and an inorganic filler, according to the present inventionconsists of 10.1-80.1% by weight of vinylester resin, 6.4-46.6% byweight of waste phosphogypsum, 5.5-42.1% by weight of magnetite,0.58-3.9% by weight of an organic peroxide and up to 29.9% by weight ofstyrene and/or a low-molecular-weight unsaturated polyester resin.

The process according to the present invention in all its modificationsmakes it possible to manufacture materials characterized by very goodphysical and chemical properties, including a very good resistance toaggressive media, also at elevated temperatures, being also perfectlysuitable for processing by mechanical methods, including grinding,cutting and machining. Moreover, the materials can be reused as fillerswhen the goods made of them are worn out. The process according to thepresent invention allowing the utilization of large amounts of wastesresulted from the production of phosphoric acid by the wet method fromphosphorite ores and consequently protecting the environment, due to thevery good performance characteristics and a wide range of application ofthe materials according to the invention, makes it possible at the sametime to save natural raw material in many cases.

The materials according to the present invention can be optionallycombined witch order materials such as wood, metals, glass, buildingmaterials, either directly at the polymerization stage or afterpreliminary setting, using the incompletely polymerized composition.

The present invention is further described by the following exampleswhich do not limit the range of its application.

EXAMPLE I

To 2 dm³ of vinylester resin, 0.029 dm³ of 1% styrene solution of cobaltnaphthenate is added on continuous stirring and then three batches areadded in turns, 3.35 dm³ each of waste phosphogypsum previously roastedat 493-498 K for 2.3 hours, with a bulk density of 0.9 kg/dm³ andparticle size below 25 μm, the whole mixture being stirred further for15 minutes. Next, 0.13 dm³ of benzoyl peroxide is added and thecomposition is stirred for 10 minutes at most to produce 8.85 dm³ of aliquid material which if casted onto a foundation forms within 2 hours afloors with an impact strength of 1.93 kJ/m², a compression strength of114 MPa and a bending strength of 37.9 MPa, suitable for use in copperelectrorefining divisions.

EXAMPLE II

Proceeding as in Example I, the composition prior to polymerization isrubbed in a grinder for 40-50 minutes and then 0.22 dm³ of Polimal 101polyester resin is added, the whole is stirred for 10 minutes and afteradding 0.135 dm³ of benzoyl peroxide, the resultant polymerizablecomposition in a quantity of 9.05 dm³ is applied by means of a spray-gunonto internal surfaces of steel or concrete tanks for copperelectrorefining to produce in a single spray a uniform layer with athickness of 320 μm, consisting of 21.7% by weight of vinylester resin,75% by weight of waste phosphogypsum, 2.2% by weight of Polimal 101polyester resin and 1.1% by weight of benzoyl peroxide.

EXAMPLE III

To 2 dm³ of vinylester resin and 0.026 dm³ of 1% styrene solution ofcobalt naphthenate, being continuously stirred, two batches, 2 dm³ each,of previously roasted at 600-605 K phosphogypsum are added alternatelywith two batches of glass-forming oxides, 0.55 dm³ each, and then onstirring 0.2 dm³ of styrene and 0.004 dm³ of dimethylaniline are added.The resultant composition in a quantity of 5.85 dm³, after adding 0.12dm³ of cyclohexanone peroxide, is used to form weights for skin-divers.

EXAMPLE IV

Proceeding as in Example III, the composition prior to polymerization istreated with 0.003 dm³ of dimethylaniline for 0.7 hour on simultaneousrubbing, then to the whole, 0.06 dm³ of styrene and 0.1 dm³ of Polimal101 polyester resin are added. The resultant composition with a density1.869 kg/dm³, in a quantity of 5.97 dm³, after adding 0.12 dm³ ofbenzoyl peroxide, is applied, as an equivalent of baryta coating, ontothe walls of a radio-isotope chamber for wet investigations, to producein a single gun spraying a coat with a thickness of 290 μm, consistingof 23.7% by weight of vinylester resin, 32.8% by weight of wastephosphogypsum, 41% by weight of glass-forming oxides, 0.6% by weight ofstyrene, 0.9% by weight of Polimal 101 polyester resin and 1% by weightof benzoyl peroxide.

EXAMPLE V

To 4 dm³ of vinylester resin on continuous stirring, 0.047 dm³ of 2%styrene solution of cobalt naphthenate is added an then during furtherstirring three batches of waste phosphogypsum, roasted at 515-518 K, 1dm³ each and microsphere 1.3 kg each are added in turns. Finally, oncontinuous stirring, 0.005 dm³ of dimethylaniline and 0.15 dm³ ofPolimal 101 polyester resin are added. The resultant composition, afteradding 0.27 dm³ of benzoyl peroxide, is poured into moulds to producefloats to be installed in equipment used in harbours, especially forabsorbing crude oil contaminations.

EXAMPLE VI

Proceeding as in Example V and using phosphogypsum and microsphere witha particle size of below 4 μm, 0.17 dm³ of Polimal 101 polyester resinand 0.28 dm³ of benzoyl peroxide are added to prepare a polymerizablecomposition suitable for application as protective coating of shiphulls, consisting of 42.5% by weight of vinylester resin, 22% by weightof waste phosphogypsum, 31.8% by weight of microsphere, 1.45% by weightof Polimal 101 polyester resin and 2.2% by weight of benzoyl peroxide.

EXAMPLE VII

Proceeding as in Example I, three batches of dry composition in aquantity of 8 kg are added, consisting of even weight parts ofpreviously roasted at a temperature of 487-490 K waste phosphogypsum andmagnetite with a particle size of up to 15 μm, and then on continuousstirring, 0.002 dm³ of benzoyl peroxide and 0.1 dm³ of styrene areadded, completing the procedure as in Example I. The resultantpolymerizable composition, consisting of 24% by weight of vinylesterresin, 36.9% by weight of magnetite, 1% by weight of styrene and 1.2% byweight of benzoyl peroxide, is poured into moulds to produce within 5hours cores suitable for use in microelectronics.

We claim:
 1. A process for the manufacture of a material bypolymerization of a synthetic vinylester resin with inorganic filler inan anhydrous medium in the presence of known accelerants and initiatorsof polymerization, wherein:per each 100 parts by volume of vinylesterresin, treated with 0.85-1.47 parts by volume of an accelerant in theform of cobalt naphthenate in styrene, on continuous stirring, aninorganic filler in the form of waste phosphogypsum is added in aquantity of 50-900 parts by volume at least in two batches; said wastephosphogypsum having a bulk density of 0.7-0.93 kg/dm³ and a particlesize of 30 μm at most, previously roasted at a temperature not lowerthan 470 K; then on further stirring for a period of at least 0.1 hour,if necessary, addition of at least one material of the group consistingof:up to 60 parts by volume of styrene, an unsaturated polyester resin,and up to 0.2 parts by volume of dimethylaniline; after which 6.3-7.3parts by volume of a known polymerization initiator such as an organicperoxide is added to the whole composition.
 2. A process according toclaim 1, wherein as an inorganic filler, there is used a drycomposition, containing per 1 part by weight of phosphogypsum, 0.7-1.5parts by weight of glass-forming oxides, consisting mainly of lead,silicon, and barium oxides.
 3. A process according to claim 1, whereinas an inorganic filler there are added phosphogypsum and glass-formingoxides, with the weight ratio of phosphogypsum to glass-forming oxidesbeing as 1:0.7-1.5.
 4. A process according to claim 1, wherein as aninorganic filler there is used a dry composition containing per each 1part by weight of waste phosphogypsum 0.6-1.3 parts by weight by ofmagnetite.
 5. A process according to claim 1, wherein as an inorganicfiller there are added phosphogypsum and magnetite, with the weightratio of phosphogypsum to magnetite being as 1:0.6-1.3.
 6. A processaccording to claim 1 or claim 2 or claim 3 or claim 4 or claim 5,wherein the composition containing vinylester resin, an accelerant ofpolymerization and inorganic filler is processed as in the manufactureof paints and lacquers, in continuously operated grinding mills toobtain a particle size of below 7 μm, after which are added at least oneof the materials in the group consisting of up to 2.5% by volume ofstyrene and up to 5% by volume of an unsaturated polyester resinfollowed by the addition of a known polymerization initiator.
 7. Aprocess according to claim 1, wherein as an inorganic filler there isused a dry composition containing per each 1 part by weight of wastephosphogypsum 0.43-40 parts by weight of microsphere.
 8. A processaccording to claim 1, wherein as an inorganic filler there are addedphosphogypsum and microsphere, with the weight ratio of phosphogypsum tomicrosphere being as 1:0.43-45.
 9. A process according to claim 7 orclaim 8, wherein the particle size of the inorganic filler is lower than7 μm.
 10. A material comprising a polymerized composition of a syntheticresin and an inorganic filler, consisting of 11.6-77.1% by weight ofvinylester resin, 14.3-86-8% by weight of waste phosphogypsum,0.67-3.74% by weight of an organic peroxide and up to 29% by weight ofat least one material of the group consisting of styrene and anunsaturated polyester resin.
 11. A material comprising a polymerizedcomposition of a synthetic resin and an inorganic filler, consisting of10.1-79.8% by weight of vinylester resin, 5.8-43.9% by weight of wastephosphogypsum, 6.4-44.88% by weight of glass-forming oxides, 0.58-3.89%by weight of an organic peroxide and up to 29.8% by weight of at leastone material of the group consisting of styrene and an unsaturatedpolyester resin.
 12. A process comprising a polymerized composition of asynthetic resin and an inorganic filler, consisting of 7.5-88.1% byweight of vinylester resin, 0.4-39.2% by weight of waste phosphogypsum,4.6-53.5% by weight of microsphere, 0.43-4.4% by weight of an organicperoxide and up to 34.1% by weight of at least one material of the groupconsisting of styrene and an unsaturated polyester resin.
 13. A materialcomprising a polymerized composition of a synthetic resin and aninorganic filler, consisting of 10.1-80.1% by weight of vinylesterresin, 6.4-46.6% by weight of waste phosphogypsum, 5.5-42.1% by weightof magnetite, 0.58-3.9% by weight of an organic peroxide and up to 29.9%by weight of at least one material of the group consisting of styreneand an unsaturated polyester resin.